Journal of American Science, 2011;7(6) http://www.americanscience.

org

Corrosion inhibition of lysine as basic amino acid on 316L stainless steel in 0.5 M H2SO4 solution

Azza El-Sayed El-Shenawy

Department of Chemistry, Faculty of Science (Girls), Al-Azhar University, Cairo, Egypt

[email protected]

Abstract: The corrosion inhibition of 316 L stainless steel in 0.5 M H2SO4 by lysine was investigated using open-
circuit potential measurements, potentiodynamic polarization measurements and scanning electron microscopy
(SEM) techniques. The open circuit potentials were measured in the absence and presence of different
concentrations of lysine. It was found that the open circuit potential becomes more positive with increasinf the
concentration of lysine. Potentiodymanic polarization measurements showed that the presence of lysine in acidic
solution effects mainly the cathodic process and decreases the corrosion current to a great extent and shifts the
corrosion potential towards more negative values. Results revealed clearly that lysine is a good cathodic type
inhibitor for 316L stainless steel in 0.5 M H2SO4. The maximum inhibition efficiency of lysine was achieved at (7 x
10–2 M). Analyses of the surface by SEM confirm these results.
[Azza El-Sayed El-Shenawy,. Corrosion inhibition of lysine as basic amino acid on 316L stainless steel in 0.5 M
H2SO4 solution. Journal of American Science 2011; 7(6):600-605]. (ISSN: 1545-1003).
http://www.americanscience.org.

Keywords: Corrosion; inhibition; lysine; amino acid; steel; M H2SO4

1. Introduction: in 0.5 M H2SO4 solutions in absence and presence of

Stainless steel have found very wide applications different concentrations ( 5 x 10–3 – 7 x 10–2 M) of
both in modern chemical industries and other places lysine.
[1]. Since aggressive acid solutions are widely used NH2
for industrial purposes. The use of organic inhibitors
in acidic solutions is very common, particularly in H2N CH2 CH2 CH2 CH2 CH COOH
view of the high corrosion rate [2-9]. Amino acids are Diamino monocarboxylic acid (Basic amino acid)
attractive as corrosion inhibitors because they are , -diamino caproic acid (lysine).
nontoxic, relatively easy to produce with high purity All aerated test solutions were prepared
at low cost, and are soluble in aqueous media. A from distilled water at room temperature (25 + 1oC)
number of studies involving amino acids and their and analar reagent chemicals. Freshly polished
derivatives on the corrosion inhibition of iron and its electrodes were used for each run. Platinum electrode
alloys has been carried out [10, 11]. Most of the and standard calomel electrode (SCE) were used as
natural amino acids are the alpha amino acids which counter and reference electrodes. The solution
contain carboxyl and amino groups bonded to the volume was fixed at 100 ml in all experiments. The
same carbon atom. It was shown that the inhibition open circuit potentials of the metal immersed in the
action of some organic compounds is based on test solutions were mortared using the electronic
adsorption phenomenon [12]. multimeter (type ES cord-EDM – 2116). The
The object of this study is to investigate the polarization measurements were run on a
inhibition effect of lysine on 316L stainless steel in computerized potentiostat (Radiometer model volta
acidic media. Lab 40) and Volta Master 4 software. Potential scan
rate in all experiments was 2 mV/s. The morphology
2- Experimental of stainless steel surface before and after immersion
The analysis of the 316L stainless steel in the test solutions was examined by scanning
electrode is given in Table (1). electron microscope (JEOL-JSM- 5500 LV).
Table (1): The chemical composition of 316L 3- Results and Discussion
stainless steel electrode (Wt %) 3.1. Open-circuit potentials measurements
Element Si Cr Ni Mo Mn Fe
Weight % 0.56 17.28 10.57 2.62 1.14 67.83 Open circuit potentials (OCP) were
measured in the absence and presence of different
Circular electrode with working surface area concentrations (5 x 10–3- 7 x 10–2 M) of lysine in 0.5
of 1.76 Cm2 were used. Experiments were carried out M H2SO4.

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Fig. 1 represents typical curves of OCP and increasing the thickness of more stable complex
variation with time for blank acid and inhibited compound (Fe-lysine).
solutions. Steady state potential is shifted either in the On introduction of lysine into the acid
positive direction in the presence of lysine. The OCP solution, the potential shift and attainment of a stable
shift in the noble direction, suggests the formation of OCP become more noble values than those observed
a passive film that acts as a barrier for metal in the blank acid. This can be attributed to the
dissolution and reduces the corrosion rate by formation of a protective layer of lysine on the
reducing the driving force of the cathodic reaction stainless steel surface.

-60
Blank 0.5 M H2SO4
-80
0.5 M H2SO4
-100 + 0.005 M lysine
0.5 M H2SO4
+ 0.01 M lysine
EmV(SCE)

-120 0.5 M H2SO4 + 0.07 M lysine

-140

-160

-180

-200

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
Time (min.)

Fig. 1. Variation of the open circuit potential of 316 L stainless steel with time in 0.5 M H 2SO4 containing different
concentrations of lysine.

3.2- Liner Polarization NH3+ O

Fig. 2 shows the effect of lysine
concentration on the polarization curves of 316 L H2N CH2 CH2 CH2 CH2 CH C OH
stainless steel electrode. Corrosion parameters in the
absence and presence of inhibitor obtained from Protonated form
curves are given in Table 2. Generally with
increasing inhibitor concentration, the corrosion
The following equation was used to the
current density and corrosion rate decrease and
calculated inhibition efficiency (IE) from polarization
polarization resistance increases (Table 2). From the
results, it is found that, with increasing inhibitor measurements[14]:
concentration, Ecorr. shifts to more negative values are  i 
observed and it indicates that these inhibitors have IE  1   x 100
been adsorbed to cathodic areas and act as cathodic  io 
inhibitor. Thus, the amino acid presents in its Where i and io are the corrosion current densities
protonated form in acidic solution. Such protonated obtained by extrapolation of the cathodic and anodic
form is expected to be highly attracted to the cathodic Tafel lines in inhibited and uninhibited solutions,
sites on the metal surface [13]. respectively.

Table (2): Corrosion parameters, and inhibition efficiency IE for 316L stainless steel in 0.5 M H2SO4 solution in the
presence of different concentrations of lysine.
Conc. Ecorr.(mV) ICorr. Tafel slope Rp Corrosion IE%
M mA/cm2 Ba Bc cm2 rate(mm/y)
Blank -336.4 0.1300 160.8 -163.9 -208.38 1.520 -
5 x 10–3 -341.8 0.1158 138.9 -135.6 -108.59 1.354 10.9
1 x 10–2 -342.2 0.0904 114.5 -126.0 30.86 1.057 30.46
7 x 10-2 -356.3 0.0558 102.8 -119.1 100.83 0.6521 57.07

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0
0.5M H2SO4
20 0.5M H2SO4+ 0.005 M lysine
-10
0.5M H2SO4+ 0.01 M lysine
0.5M H2SO4+ 0.07 M lysine

Y Axis Title
-20

10 -30

-40
-0.75 -0.70 -0.65 -0.60 -0.55 -0.50 -0.45 -0.40 -0.35 -0.30
X Axis Title

0
urrentdensity[mA/cm]
2

-10

-20
C

-30

-40
-1.0 -0.5 0.0 0.5 1.0 1.5
Potential ( V)

(a)
0.005M Lysine+0.5M H2SO4
0.05M Lysine+0.5M H2SO4
0.07M Lysine+0.5M H2SO4
0.5M H2SO4
0

-2
log I(mA/cm )
2

-4

-6

-8

-10
-600 -500 -400 -300 -200 -100
Potential (V)

(b)

Fig.2. Cathodic and anodic polarization curves for the effect of different concentrations of lysine on the
potentiodynamic behaviour of 316L stainless steel in 0.5 M H 2SO4 solution.

and corrosion rate decrease as shown in Fig. 3 (a and

The inhibition efficiency increases as the inhibitior b).
concentration increases and reaches maximum values
of 57.07% at 7 x 10–2 M. Generally with increasing
inhibitor concentration, the corrosion current density

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0.3

0.25

Icorr. mA/cm2
0.2

0.15

0.1

0.05

0
-5
5 x 10
1 1 x210-2 1.5 x3 10-2 7 x 410-2
(a)
Conc. of Lysine (M)

1.5
Corr. rate mm/y

0.5

0
1 5 x 10-5 1 x 210-2 1.5 x 310-2 7 x 410-2

(b)
Conc. of Lysine (M)

Fig. 3. Effect of lysine concentration on Icorr.(a), and on corrosion rate (b) of 316L stainless steel electrode in
0.5 M H2SO4 solution.
The adsorption mechanism for a given
It is clear from the potentiodynamic inhibitor depends on such factors, as the nature of
polarization experiments that, the presence of lysine metal corrosion medium, the pH and the
decreases the corrosion rate, i.e. the value of Icorr concentration of the inhibitor as well as the functional
decreases. Particularly, the cathodic reaction is groups present in its molecule [15]. The corrosion
inhibited to larger extent than the anodic reaction. inhibition process is based on the adsorption of the
Since the transfer of oxygen from the bulk solution to amino acid molecules on the active sites and/or
the stainless steel/solution interface will strongly deposition of the corrosion products on the alloy
affect the rate of oxygen reduction, it can be inferred surface [16,17]. Thus it is possible to suggest that at
that the adsorbed layer behaves as a cathodic low concentration, the amount of lysine in the
inhibitor to 316L stainless steel corrosion by solution was insufficient to form a compact complex
retarding the transfer of O2 to the cathodic sites of the with the metal ions, so that the resulting adsorbed
316L stainless steel surface. intermediate was readily soluble in the acidic
The cathodic peaks observed at -750 mV, environment. As the concentration is increased, more
which increase in number by increasing the lysine molecules become available for complex
concentration of lysine. formation, which subsequently diminishes the
solubility of the surface layer, leading to improved
3-3- The inhibition mechanism inhibiting effect [15].

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The increase in efficiency of inhibition with The adsorption behaviour of various amino
concentration indicates that more lysine molecules acids on 316L stainless steel surface was investigated
are adsorbed on the metal surface at higher [19]. These investigations suggest that the acidic and
concentration, leading to greater surface coverage. basic amino acids are adsorbed through two
The reduced effectiveness is observed at low electrostatic interactions of two ionized groups in the
inhibitor concentrations, including the relatively amino acid with 316L stainless steel surface.
small molecular area of lysine. It is generally However, it has been reported that the number of –
accepted that the first step in the adsorption of an OH groups on the stainless steel surface is nearly the
organic inhibitor on a metal surface usually involves same regardless of the crystal forms of the metal
the replacement of one or more water molecules oxide on the surface and thickness of the passive
adsorbed at the metal surface [18]. films [20,21]. The calculated configurations for the
basic amino acids such as lysine and arginine show
Inh(sol.) + x H2O(ads.) Inh(ads.) + x H2O(sol.)
that the symmetric axis of –NH3+ groups and the
The inhibitor may then combine with freshly
guanidine groups of the basic amino acids are
generated Fe2+ ions on the stainless steel surface,
directed to O–. Such orientations of the anionic and
forming metal - inhibitor complex(18):
cationic groups of the acidic and basic amino acids
Fe Fe2+ + 2e–
2+ were quite consistent with those indicated by the
Fe + Inh(ads.) [Fe-Inh]2+(ads.)
results from FT-IR analyses [19].

(a) (b)

(c) (d)
Fig. 4. SEM images of 316L stainless steel surface at 200 magnification, (a) polished surface, (b) stainless steel surface
after immersion 2 hr in 0.5 M H2SO4 solution without lysine, (c) stainless steel surface after immersion 2 hr in 0.5
M H2SO4 containing 5 x10–3 M lysine,(d) stainless steel surface after immersion 2 hr in 0.5 M H2SO4 containing 7
x 10–2 M lysine.

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3. S.L. Graness, B.M. Rosales, C. Oviedo, J.O.

3-4- SEM analysis Zerbino, Corrosion Science, 33 (9); (1992) 1439.
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The surface morphology of 316L stainless Corrosion 49(6); (1992) 343.
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(SEM), surface was observed after 2 hs of immersion Lagrenee, Corrosion Science 40(2-3); (1998) 391.
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being exposed to the testing environment, it was 8. M. Bouayed, H. Rabaa, A. Srhiri, J.Y. Saillard, A.
observed as a uniform surface along with the Benbachir, A. Lebeuze, Corroson Science 41;
presence of dark spots. Fig. 4b shows the SEM image (1999) 501.
after immersion in 0.5 M H2SO4 (Blank solution) 9. M.A. Elmorsi, Corrosion Science 41; (1999) 305.
without lysine, showing presence of small number of 10. G. Moretti, F. Guidi, G. Grion, Corrosion Science
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(5 x 10–3& 7 x 10–2) of lysine , respectively. It is
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17. G.Bereket, A. Yurt, Corrosion Science 43; (2001)
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19. Koreyoshi Imamura, Tomoya Mimura, Makoto
4- Conclusion Okamoto, Takaharu Sakiyama, Kazuhiro
From the above studies, it can be concluded that: Nakanishi, J. Colloid Interface Science 229; (2000)
1- Lysine is a good cathodic inhibitor for corrosion 237.
of stainless steel in 0.5 M H2SO4 solution. 20. S.Kittaka, J. Colloid Interface Science 48;(1974)
2- Corrosion inhibition efficiency of lysine 327.
increases with increasing its concentration and 21. S.Kittaka, J. Colloid Interface Science 48; (1974)
reaches a maximum value at 7 x 10-2 M. 334.
3- Corrosion inhibition by lysine takes place by 22. S.A.M. Refaey, F.Taha, A.M.Abd El-Malak,
adsorption of the inhibitor on the metal surface Applied Surface Science 236, (2004) 175.
and formation of a protective layer (Fe-lysine
complex film) on the metal surface. 5/23/2011
4- The SEM images confirm the inhibitive character
of lysine and the degree of inhibition increases
with increase in concentration.

Corresponding author
Azza El-Sayed El-Shenawy
Department of Chemistry, Faculty of Science (Girls),
Al-Azhar University, Cairo, Egypt
[email protected]

References
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2. L. Singh, corrosion, 49 (6); (1993) 473.

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